hetcateng workshop ustutt

8/12/2019 HetCatEng Workshop USTUTT

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INSTITUTE OFCHEMICAL TECHNOLOGY

Heterogeneous Catalysis Engineering

E. Klemm

Topical Workshop Catalysis

DFG Priority Program 1362

Stuttgart, April 12, 2011


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Outline

What is Heterogeneous Catalysis Engineering ?

Bulk Chemicals Manufacture

Space Time Yield

Selectivity-Conversion-Plots

Catalyst Life Time

Fine Chemicals Manufacture

Space Time Yield

Atom Efficiency (E Factor) Time-to-Market

Bench Scale Reactors for Het. Cat. Eng.


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Surface

Science

Reaction

Engineering

Operando Spectroscopy

Quantum Mechanics / DFT

Time Scale

Length Scale

Process

Engineering

ProductionLevel

Reaction Kinetics

Reactor Modelling

Scale-up

Separation units

Recycle

Quality Control

Longterm Stability

Material and

Pressure Gap

Heterogeneous

CatalysisResearch

HeterogeneousCatalysis Engineering

Heterogeneous

Catalysis

Research

Heterogeneous

Catalysis

Engineering


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Act ivit y

Selectivity

ActiveSite

CatalystPellet

Reactor Process

TurnoverFrequency

EffectiveReaction Rate

Conversion /Space Time Yield

ProcessConversion

DifferentialSelectivity

on Active Site

DifferentialSelectivityon Pellet

IntegralSelectivity

ProcessSelectivity

ReactorScale

E

E+P+SP

MolecularScale

E P

PSP

ParticleScale

E P+SP

SP

E

E+P+SP

P+SP

P

E

Purge

ProcessScale


Heterogeneous

Catalysis Research

HeterogeneousCatalysis Engineering


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time

Bench Scale

Experiments

Feasibility

Study

time

Space Time Yield,

Selectivity/Conversion,

catalyst life time etc.

Market Analysis

Profitability (CAPEX, OPEX)

Preliminary Flow Sheet

Technical Reactor ConceptFront End

Engineering

Basic

Engineering

Detailed Flow Sheet

Dimensioning of Apparatuses

Expenditure Estimation (CAPEX, OPEX)

Detailed

Engineering

Measuring and Control

Dimensioning of Pipes

Ordering

Mechanical

Completion Erection of Plant

Commisioning Commisoning

Heterogeneous

Catalysis

Engineering

(University/

Industry)

Heterogeneous

Catalysis

Engineering

(Industry)

Start of

Production

Start of

Production


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The bench scale results were so good that we by-passed the pilot-plantaus E.H. Stitt, Chem.Eng.J. 90(2002)47


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Bulk Chemicals Fine Chemicals

Plant Capacity > 10,000 metric tons per year(usually: some 100,000 t/a)

< 10,000 metric tons per year(usually < 1,000 t/a)

Space Time Yield 1-10 kilogram perliter and hour

0.01-1 kilogram perliter and hour

Processing continuous batch-wise

Phase gas (liquid) liquidReactor typically tube typically stirred tank

Plant dedicated multi-purpose

Product price < 10 $/kg > 10 $/kg

Lifecycle of product long relatively short

Added value low high

Raw materials quote high low

kg waste / kg product(E Factor)

relatively low(< 1-5)

high(5-50)


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Outline



Space Time Yield

Selectivity-Conversion-Plots

Catalyst-Life-Time


Space-Time-Yield

Atom Efficiency (E Factor) Time-to-Market

Bench Scale Reactors for Het. Cat. Eng.


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Act ivit y

Selectivity

ActiveSite

CatalystPellet

Reactor Process

TurnoverFrequency

EffectiveReaction Rate

Conversion /Space Time Yield

ProcessConversion


on Active Site


on Pellet

IntegralSelectivity

ProcessSelectivity

ReactorScale

E

E+P+SP

MolecularScale

E P

P SP

ParticleScale

E P+SP

SP

E

E+P+SP

P+SP

P

E

Purge

ProcessScale


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Process Profitability =

f(Reactor Costs, Separation Costs, Recycle Costs, Feedstock Costs)

Separation Costs

= f(Selectivity)Recycle Costs

= f(Conversion)

E+P+SP

E

E

P+SP

P

SP

Reactor Costs

= f(Space Time Yield)

Feedstock Costs

= f(Selectivity)

CAPEX OPEX


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Process Profitability = f(Selectivity-Conversion-Plot , )

Educt Product Side Product

Molecular Scale:

Turnover Frequencies

Reducing Formation of Side Products

Particle Scale:

Avoiding Film and Pore Diffusion

Limitation

Utilization of Shape Selective Effects

Reactor Scale:

Avoiding Backmixing Avoiding Hot Spots

Process Scale:

Recycle of Educt

Integration of Separation


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with increasing conversion the selectivity decreases-> feed-stock costs increase

with increasing conversion less educt has to be

separated and recycled

-> energy costs decrease

Xopt


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13Source: SRI Consulting

Reactor


CH3

OH

O

CH2

CH2

CH3

OCH

CH2

O

+ + + H2OPd/Au

0,5 O2

VAMXC2H4 = 8-10 %XHAc = 15-35 % SVAM,C2H4 = 88-96 %


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Process Profitability = f(Reactor Costs,)

E+P+SP

E

E

P+SP

P

SP

Reactor Costs

= f(Space Time Yield)


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f(Space Time Yield (STY), )

=

=

==

h

Product

Reac

,

reac

,

reac

l

kgMSXc

V

MSXcV

V

mSTY

PEPEEo

PEPEEoP

Typical Values of STY:

1-10 kg product per 1 liter reaction volume

and hour

Residence Time


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Space Time Yield

(STY):

Het. Catalysis: 1-10 kg/(lh)

Hom. Catalysis: 0.01 1 kg/(lh)

Biocatalysis: 0.001 0.01 kg/(lh)

hourandvolumereactionofliter

productofkilogram

Reaction

temp.

Cat.

conc.


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Process Profitability = f(Space Time Yield (STY), )

Wird beim Arbeiten im Kreislauf jeweils nur ein geringer Umsatz

der Reaktionsgase Stickstoff und Wasserstoff erreicht, so ist es

von grter technischer und wirtschaftlicher Bedeutung ,diese geringfgige Umsetzung noch bei schnellem

Durchleiten, also kurzer Berhrungszeit der Gase mit dem

Katalysator zu erreichen. Solch reiche Raum-Zeit-Ausbeute

ist nun nur mit Katalysatoren erreichbar, die den um 1905

bekannten an Wirksamkeit um ein Vielfaches berlegen sind.

Alwin Mittasch, Geschichte der Ammoniaksynthese, Verlag Chemie, Weinheim 1951.


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undesired

time on stream (tos)

or process time

usually:

catalyst life time at least 8.000 hrs. (1 year)

catalyst activity


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Bulk Chemicals Manufacture (Example I)

Direct Ring Oxidation of Aromatics with N2O(E. Klemm et al., Direct Ring Oxidation of Aromatics, in: G. Ertl, H. Knzinger, J. Weitkamp (Hg.), Handbook of HeterogeneousCatalysis, 2nd edition, WILEY-VCH, Weinheim, 2008)

A+B+NP

B+NP

NP

B

A

Purge

A B

A

A+B+NP

B NP

A B+NP

A

Strong adsorption and slow

diffusion of product

compared to educt !

0

20

40

60

80

100

0 2 4 6 8 10 12

Verhltnis Benzol:N2O

SelektivittN2O

zuPhenol[%]

Solutia:


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Bulk Chemicals Manufacture (Example II: DEMiS)

equal

up

E. Klemm et al., Ind. Eng. Chem. Res. 2008, 47, 2086.

gas

TS-1 cat.

3 cm

Labor

Ti O SiH

2O

2

Si

OH

olefin

Si

OH

epoxid

HO

Ti

O

Si

OH

HO

Ti

O

OH

Ti

H2O

TS-1

hydroperoxidspecies

oxygen transfer

dehydratation

Foto: TU-Chemnitz

Lab Scale

1 m

0,6 m

Industrieller Mastab

Foto: Uhde GmbH / Degussa AG

Pilot Scale


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According to: E. Ananieva, A. Reitzmann, Chem. Eng. Sci., 59 (2004) 5509 - 5517


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3 8hydrogen peroxide

in gas [vol%]

>1substrate/hydrogen

peroxide

1reaction pressure

[bar]

100-150

reaction temperature[C]

Reaction conditions

Catalyst TS-1

3 8hydrogen peroxide

in gas [vol%]

>1substrate/hydrogen

peroxide

1reaction pressure

[bar]

100-150


Reaction conditions

Catalyst TS-1

0

20

40

60

80

100

0 20 40 60 80 100

X (propene) / %

S(propyleneoxide,

prope

ne)/%

Lab scale fixed bed (C3H6/H2O2=1,0)

Lab scale micro reactor (C3H6/H2O2=1,4)


Pilot scale micro reactor (C3H6/H2O2=1,4)


gas

TS-1 cat.


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3 8hydrogen peroxidein gas [vol%]

>1substrate/hydrogenperoxide

1reaction pressure[bar]

100-150


Reaction conditions

Catalyst TS-1

3 8hydrogen peroxidein gas [vol%]

>1substrate/hydrogenperoxide

1reaction pressure[bar]

100-150


Reaction conditions

Catalyst TS-1

0

20

40

60

80

100

0 20 40 60 80 100

X (H2O2) / %

S(pro

pyleneoxide,

H2O

2)/%

Lab scale fixed bed (C3H6/H2O2=1,0)





gas

TS-1 cat.


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E. Klemm, G. Mathivanan, T. Schwarz, S. Schirrmeister,

Evaporation of Hydrogen Peroxide with a Microstructured

Falling Film, Chem. Eng. Proc, submitted.

E. Klemm et al.,

Method for Obtaining a Gaseoues Phase From a Liquid

Medium and Device for Carrying Out the Same,

Disclosure WO 2004/036137 A2, 29.04.2004.

gas

TS-1 cat.

S. Heinrich, M. Plettig, E. Klemm,Role of the Ti(IV)-Superoxide Species in the Selective

Oxidation of Alkanes with Hydrogen Peroxide in the Gas

Phase on Titanium Silicalite-1 an In-Situ EPR

Investigation Catal. Lett. 141(2011)251.

T. Schwarz, S. Schirrmeister, H. Dring, E. Klemm,

Herstellung von Wandkatalysatoren fr Mikrostruktur-

reaktoren mittels der Niederdruckspritztechnologie,

Chem. Ing. Tech. 82(2010)921.

S. Schirrmeister, K. Bker, M. Schmitz-Niederau, B.

Langanke, A. Geielmann, F. Becker, R. Machnik, G.

Markowz, T. Schwarz, E. Klemm,

Katalytisch beschichtete Trger, Verfahren zu dessen

Herstellung und damit ausgestatteter Reaktor sowie

dessen Verwendung,

Disclosure DE 10 2005 019 000 A1, 26.10.2006.

E. Klemm et al., Ind. Eng. Chem. Res. 2008, 47, 2086.


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Virtual, but realistic example:

Fine chemical synthesis with YP,E=80 %, cEo = 1 mol/land MP = 100 g/mol

(assuming stirred tank reactor witch Vreac = 2 m3)

3-shift batch-wise operation:

Production Capacity: ca. 170 t / a

Space Time Yield: ca. 0.01 kg per liter and hour

daykgmolglmoll

MYcVm EPEoreac

/480/1008.0/1000,23

3 P,yProduct/da

=

==

==


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f(Space Time Yield (STY), )

=

=

=

=

hProduct

Reac

,

Reac

,Reac

Reac

l

kg

t

MYc

tV

MYcV

tV

mSTY

PEPEo

PEPEoP

Process Time

for batch-wise

operation

Typical Values of STY:

0.01 1 kg product per 1 liter reaction

volume and hour


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Space Time Yield

(STY):

Het. Catalysis: 1-10 kg/(lh)

Hom. Catalysis: 0.01 1 kg/(lh)

Biocatalysis: 0.001 0.01 kg/(lh)

hourandvolumereactionofliter

productofkilogram

Reaction

temp.

Cat.

conc.


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Plant Capacity E Factor(kg waste / kg product)

Oil Refining > 1 Mio t / year < 0.1

Bulk Chemicals 10.000 t / year

up to1 Mio t / vear

< 1-5

Fine Chemicals < 10.000 t / year 5-50

Pharmaceuticals < 1 t / year 25-100

According to: R.A. Sheldon, The E factor: fifteen years on, Green Chemistry 9 (2007) 1273.

Process Development for the Reduction of the E factorin Fine

Chemicals and Pharmaceuticals Manufacture due to

reduction of negative environmental impact

reduction of cost of disposing of waste


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From: A. Stankiewicz, Process Intensification Workshop, DECHEMA, 29.05.2006.

Process time in batch-wise fine chemical manufacture is mostlylimited by heat and mass, and not by the chemical reaction itself.

Due to increasing V and decreasing A/V, process time increases

when scaling up from bench to production scale.


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From: Dr. J. Lang, Evonik Degussa

26 cm

36 cm

Granulatdosierung

Zerkleinern/Feinmahlen

Granulatspeicher

Feinkorndosierung

Lsemittelpuffer

Flssigdosierung

berhitzung

Druckdosierung

Filtration

Filterkuchenaustrag

Rckstandspeicher Produkt

Extraktion

310 ml

48 sec

23 L/h

204 tons/year

V=ca. 40 l


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Shifting from batch-wise to continuous operation:

Fine chemical synthesis with YP,E=80 %, cE0 = 1 mol/land MP = 100 g/mol

(assuming continuous reactor with Vreac = 40 l and

reaction time of 1 min):

Production Capacity: ca. 1,533 t / a

Space Time Yield: ca. 4.8 kg per liter and hour

higher capacity or shorter time-to-market

daytdaykg

molglmoll

MYcVm

EPEo

/6,4/608,4

min1

/1008.0/140

P,reac

Product

==

=

=

==


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32J. Yoshida, A. Naganki, T. Yamada, Chem. Euro. J. 14(2008)7450.



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Bench Scale Reactors for Heterogeneous Catalysis

Catalytic Wall

Reactors

TubeReactor

Recycle

Reactor

(Type Berty)

Stirred Autoclave Reactor

Source:

Lehrstuhl Technische Chemie,

Universitt Erlangen-NrnbergUniversitt Stuttgart

Slug Flow Reactor


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List of Symbols

Symbol Dimension Description

cE,0 mol m-3

concentration of educt species E at the beginning of the reaction

ME g mol-1

molar mass of educt E

Pm kg s-1

productivity (mass flow of the product P)

SP,E - selectivity to product P related to educt Et s process time

Vreac m3 reaction volume

V m3s

-1 volumetric flow rate

XE - conversion of educt E

YP,E - yield of product P related to educt E

s residence time

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